ATBECHDEDKESFRGBGRITLILUNLSEMCPTIESILTLVFIRO..CY..TRBGCZEEHUPLSK....IS..............................JDIM360 Ver 2.15 (14 Jul 2008) - 2100000/01785429EUROPEAN PATENT SPECIFICATIONB120121003EP05766182.9200507112007022320110125jaenen200424964920040830JP20121003201240200705162007202012100320124020120319C07F 17/00 20060101AFI20060401BHEP C07F 7/28 20060101ALI20100419BHEP C08F 4/64 20060101ALI20100419BHEP deVERFAHREN ZUR HERSTELLUNG EINER METALLOCENVERBINDUNGenPROCESS FOR PRODUCING METALLOCENE COMPOUNDfrPROCÉDÉ SERVANT À PRODUIRE UN COMPOSÉ MÉTALLOCÈNERAU, ALEXANDER ET AL: "Synthesis and application in high-pressure polymerization of a titanium complex with a linked cyclopentadienyl-phenoxide ligand" JOURNAL OF ORGANOMETALLIC CHEMISTRY , 608(1-2), 71-75 CODEN: JORCAI; ISSN: 0022-328X, 2000, XP002578026MA H. ET AL: 'Synhteses and X-ray structures of half-sandwich o-methoxylbenzyl-indenyl zirconium complexes with coordinated THF.' INORGANIC CHEMISTRY COMMUNICATIONS. vol. 4, no. 9, 2001, pages 515 - 519, XP002991097WANG J. ET AL: 'Synthesis, characterization and catalysis of (n5, n1-C5H4-CHPh-PhO)TiC12.' CHEMICAL RESEARCH IN CHINESE UNIVERSITIES. vol. 17, no. 1, 2001, pages 115 - 116, XP00299109820100426SENDA, Taichi23-5-108, Minamiakutagawa-choTakatsuki-shi, OsakaJPHIDA, Noriyuki7-2-20-305, Nakamikunigaoka-choSakai-ku, Sakai-shi, OsakaJPHANAOKA, Hidenori5-3-18-306, FuruedaiSuita-shi, Osaka 5650874JPSumitomo Chemical Company, Limited100229295N 1327 EP27-1, Shinkawa 2-chome, Chuo-kuTokyo 104-8260JPVossius & Partner100751388Siebertstrasse 481675 MünchenDEATBEBGCHCYCZDEDKEEESFIFRGBGRHUIEISITLILTLULVMCNLPLPTROSESISKTRJP200501319720050711jaWO20060251592006030920061020070516200720

The invention relates to a process for producing a metallocene compound.

Metallocene complexes are useful as one component of polymerization catalysts to be used for olefin polymerization and a large number of metallocene complexes have been reported. Particularly, a bridged half metallocene complexes having a ligand consisting of cyclopentadiene and phenol bridged by a Group 14 atom of the Periodic Table is highly expected as a metal complexes to have unique activity owing to the unique structure among the metallocene complexes (e.g., reference to Patent Document 1). The process of producing the bridged half metallocene complexes generally involves generation of an anion from a ligand by reacting the ligand with a base and reacting the resulting anion with a metal complex precursor, however it has been desired to develop an industrially advantageous method.

In Non-Patent Document 2 the synthesis of [hsin1-C5H4-CHP4-Pho]TiCl2 is disclosed.]

Patent Document 1: Japanese Patent Application Laid-Open (JP-A) No. 9-87313

Non-Patent Document 1: J. Organomet. Chem. 2000, 608, 71-75

Non-Patent Document 2: Wang J.-H. et al., Chemical Research in Chinese Universities 2001, 17(1), 115-116.

The invention relates to an improved and more advantageous process for producing a metallocene compound.

The invention provides a process for producing a metallocene compound of formula (3) wherein R1, R2, R3 and R4 independently denote

Hereinafter, the invention will be described more in detail.

In compounds of the invention, a halogen atom represented by R1, R2, R3,R4, R5,R6, R7, R8, R9, R10, R12, R13, R14, X1, X2, X3, X4, X5, or X6 include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and preferred is a chlorine atom.

The substituent group of the substituted C1-20 alkyl group represented by R1, R3, R4, R5, R6, R7, R8, R9, R10, X1, X2, X3, X4, X5, or X6 include, for example, a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom. Specific examples of the substituted or unsubstituted alkyl are methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, neopentyl, amyl, n-hexyl, heptyl, n-octyl, n-nonyl, n-decyl, n-dodecyl, n-tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, n-eicosyl, fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, bromomethyl, dibromomethyl, tribromomethyl, iodomethyl, diiodomethyl, triiodomethyl, fluoroethyl, difluoroethyl, trifluoroethyl, tetrafluoroethyl, pentafluoroethyl, chloroethyl, dichloroethyl, trichloroethyl, tetrachloroethyl, pentachloroethyl, bromoethyl, dibromoethyl, tribromoethyl, tetrabromoethyl, pentabromoethyl, perfluoropropyl, perfluorobutyl,perfluoropentyl, perfluorohexyl, perfluorooctyl, perfluorododecyl, perfluoropentadecyl, perfluoroeicosyl, perchloropropyl, perchlorobutyl, perchloropentyl, perchlorohexyl, perchlorooctyl, perchlorododecyl, perchloropentadecyl, perchloroeicosyl, perbromopropyl, perbromobutyl, perbromopentyl, perbromohexyl, perbromooctyl, perbromododecyl, perbromopentadecyl, and perbromoeicosyl and preferred examples are methyl, ethyl, isopropyl, tert-butyl, and amyl.

Specific examples of the unsubstituted C7-20 aralkyl represented by R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, X1, X2, X3, X4, X5, or X6 include, benzyl, (2-methylphenyl)methyl, (3-methylphenyl)methyl, (4-methylphenyl)methyl, (2,3-dimethylphenyl)methyl, (2,4-dimethylphenyl)methyl, (2,5-dimethylphenyl)methyl, (2,6-dimethylphenyl)methyl, (3,4-dimethylphenyl)methyl, (4,6-dimethylphenyl)methyl, (2,3,4-trimethylphenyl)methyl, (2,3,5-trimethylphenyl)methyl, (2,3,6-trimethylphenyl)methyl, (3,4,5-trimethylphenyl)methyl, (2,3,6-trimethylphenyl)methyl, (2,3,4,5-tetramethylphenyl)methyl, (2,3,4,6-tetramethylphenyl)methyl, (2,3,5,6-tetramethylphenyl)methyl, (pentamethylphenyl)methyl, (ethylphenyl)methyl, (n-propylphenyl)methyl, (isopropylphenyl)methyl, (n-butylphenyl)methyl, (sec-butylphenyl)methyl, (tert-butylphenyl)methyl, (n-pentylphenyl)methyl, (neopentylphenyl)methyl, (n-hexylphenyl)methyl, (n-octylphenyl)methyl, (n-decylphenyl)methyl, (n-decylphenyl)methyl, naphthylmethyl, and anthracenylmethyl, and preferred is benzyl.

Examples of the substituted C7-20 aralkyl include those exemplified as unsubstituted C7-20 aralkyl groups substituted with a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom as a substituent.

Specific examples of the unsubstituted C6-20 aryl represented by R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, X1, X2, X3, X4, X5, or X6 include phenyl, 2-tolyl, 3-tolyl, 4-tolyl, 2,3-xylyl, 2,4-xylyl, 2,5-xylyl, 2,6-xylyl, 3,4-xylyl, 3,5-xylyl, 2,3,4-trimethylphenyl, 2,3,5-trimethylphenyl, 2,3,6-trimethylphenyl, 2,4,6-trimethylphenyl, 3,4,5-trimethylphenyl, 2,3,4,5-tetramethylphenyl, 2,3,4,6-tetramethylphenyl, 2,3,5,6-tetramethylphenyl, pentamethylphenyl, ethylphenyl, n-propylphenyl, isopropylphenyl, n-butylphenyl, sec-butylphenyl, tert-butylphenyl, n-pentylphenyl, neopentylphenyl, n-hexylphenyl, n-octylphenyl, n-decylphenyl, n-dodecylphenyl, n-tetradecylphenyl, naphthyl, and anthracenyl, and preferably phenyl.

Examples of the substituted C6-20 aryl include these exemplified as the unsubstituted C6-20 aryl groups substituted with a halogen atom such as a fluorine atom, chlorine atom, a bromine atom, or an iodine atom as a substituent.

Specific examples of the unsubstituted C1-20 hydrocarbon in the silyl having a substituted or unsubstituted C1-20 hydrocarbon represented by R5, R6, R7, R8, R9, or R10 are a C1-10 alkyl such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, isobutyl, n-pentyl, n-hexyl, cyclohexyl, n-heptyl, n-octyl, n-nonyl, or n-decyl; and an aryl such as phenyl and these substituent groups may be bonded one another to form rings.

Specific examples of the substituted silyl having the unsubstituted C1-20 hydrocarbon as a substituent group are mono-C1-20 hydrocarbon substituted a silyl group such as methylsilyl, ethylsilyl, and phenylsilyl; a di-C1-20 hydrocarbon substituted silyl group such as dimethylsilyl, diethylsilyl, and diphenylsilyl; a tri-C1-20 hydrocarbon substituted silyl such as trimethylsilyl, triethylsilyl, tri-n-propylsilyl, triisopropylsilyl, tri-n-butylsilyl, tri-sec-butylsilyl, tri-tert-butylsilyl, triisobutylsilyl, tert-butyldimethylsilyl, tri-n-pentylsilyl, tri-n-hexylsilyl, tricyclohexylsilyl, and triphenylsilyl; and a cyclic silyl having substituent groups forming a ring such as cyclotrimethylenemethylsilyl, cyclotetramethylenemethylsilyl, cyclopentamethylenemethylsilyl, cyclotrimethylenephenylsilyl, cyclotetramethylenephenylsilyl, and cyclopentamethylenephenylsilyl and preferably trimethylsilyl, tert-butyldimethylsilyl, and triphenylsilyl. Examples of the hydrocarbon group composing these substituted silyl groups may also include substituted C1-20 hydrocarbon having, as a substituent, a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, and a iodine atom, besides the above exemplified unsubstituted hydrocarbon groups.

Specific examples of the unsubstituted C1-20 alkoxy represented by R5, R6, R7, R8, R9, R10, X1, X2, X3, X4, X5, or X6 are methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, tert-butoxy, n-pentyloxy, neopentyloxy, n-hexyloxy, n-octyloxy, n-nonyloxy, n-decyloxy, n-dodecyloxy, n-undecyloxy, n-dodecyloxy, tridecyloxy, tetradecyloxy, n-pentadecyloxy, hexadecyloxy, heptadecyloxy, octadecyloxy, nonadecyloxy, or n-eicosyloxy, and preferred are methoxy, ethoxy, and tert-butoxy.

Examples of the substituted C1-20 alkoxy include those exemplified as unsubstituted C1-20 alkoxy groups substituted with a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom as a substituent.

Specific examples of the unsubstituted C7-20 aralkyloxy represented by R5, R6, R7, R8, R9, R10, X1, X2, X3, X4, X5, or X6 are benzyloxy, (2-methylphenyl)methoxy, (3-methylphenyl)methoxy, (4-methylphenyl)methoxy, (2,3-dimethylphenyl)methoxy, (2,4-dimethylphenyl)methoxy, (2,5-dimethylphenyl)methoxy, (2,6-dimethylphenyl)methoxy, (3,4-dimethylphenyl)methoxy, (3,5-dimethylphenyl)methoxy, (2,3,4-trimethylphenyl)methoxy, (2,3,5-trimethylphenyl)methoxy, (2,3,6-trimethylphenyl)methoxy, (2,4,5-trimethylphenyl)methoxy, (2,4,6-trimethylphenyl)methoxy, (3,4,5-trimethylphenyl)methoxy, (2,3,4,5-tetramethylphenyl)methoxy, (2,3,4,6-tetramethylphenyl)methoxy, (2,3,5,6-tetramethylphenyl)methoxy, (pentamethylphenyl)methoxy, (ethylphenyl)methoxy, (n-propylphenyl)methoxy, (isopropylphenyl)methoxy, (n-butylphenyl)methoxy, (sec-butylphenyl)methoxy, (tert-butylphenyl)methoxy, (n-hexylphenyl)methoxy, (n-octylphenyl)methoxy, (n-decylphenyl)methoxy, naphthylmethoxy, and anthracenylmethoxy, and preferably benzyloxy.

Examples of the substituted C7-20 aralkyloxy include these exemplified as the unsubstituted C7-20 aralkyloxy groups substituted with a halogen atom such as a fluorine atom, chlorine atom, a bromine atom, or an iodine atom as a substituent.

Specific examples of the unsubstituted C6-20 aryloxy represented by R5, R6, R7, R8, R9, R10, X1, X2, X3, X4, X5, and X6 include phenoxy, 2-methylphenoxy, 3-methylphenoxy, 4-methylphenoxy, 2,3-dimethylphenoxy, 2,4-dimethylphenoxy, 2,5-dimethylphenoxy, 2,6-dimethylphenoxy, 3,4-dimethylphenoxy, 3,5-dimethylphenoxy, 2,3,4-trimethylphenoxy, 2,3,5-trimethylphenoxy, 2,3,6-trimethylphenoxy, 2,4,5-trimethylphenoxy, 2,4,6-trimethylphenoxy, 3,4,5-trimethylphenoxy, 2,3,4,5-tetramethylphenoxy, 2,3,4,6-tetramethylphenoxy, 2,3,5,6-tetramethylphenoxy, pentamethylphenoxy, ethylphenoxy, n-propylphenoxy, isopropylphenoxy, n-butylphenoxy, sec-butylphenoxy, tert-butylphenoxy, n-hexylphenoxy, n-octylphenoxy, n-decylphenoxy, n-tetradecylphenoxy, naphthoxy, and anthracenoxy, and preferred is phenoxy.

Examples of the substituted C6-20 aryloxy include those exemplified as unsubstituted C6-20 aryloxy groups substituted with a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom as a substituent.

The amino substituted with a substituted or unsubstituted C1-20 hydrocarbon group represented by R5, R6, R7, R8, R9, R10, X1, X2, X3, X4, X5, or X6 is an amino group di-substituted with substituted or unsubstituted C1-20 hydrocarbon groups, and examples of the unsubstituted C1-20 hydrocarbon group include a C1-20 alkyl such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, isobutyl, n-pentyl, n-hexyl, or cyclohexyl; and an aryl such as phenyl and these substituent groups may be bonded one another to form rings.

Examples of the amino group substituted with the unsubstituted C1-20 hydrocarbon groups include dimethylamino, diethylamino, di-n-propylamino, diisopropylamine, di-n-butylamino, di-sec-butylamino, di-tert-butylamino, di-isobutylamino, tert-butylisopropylamino, di-n-hexylamino, di-n-octylamino, di-n-decylamino, diphenylamino, bistrimethylsilylamino, bis(tert-butyldimethylsilyl)amino, pyrrolyl, pyrrolidinyl, piperidinyl, carbazolyl, dihydroindolyl, and dihydroisoindolyl and preferably dimethylamino, diethylamino, pyrrolidinyl, and piperidinyl.

Examples of the substituted C1-20 hydrocarbon group include those exemplified as C1-20 hydrocarbon groups substituted with a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom as a substituent.

The silyloxy substituted with a substituted or unsubstituted C1-20 hydrocarbon group represented by R5, R6, R7, R8, R9, or R10 is a silyloxy group substituted with substituted or unsubstituted C1-20 hydrocarbon groups, and examples of the unsubstituted C1-20 hydrocarbon group include the above-exemplified C1-20 alkyl such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, isobutyl, n-pentyl, n-hexyl, or cyclohexyl; and an aryl such as phenyl, and these substituent groups may be bonded one another to form rings.

Examples of the silyloxy group substituted with the unsubstituted C1-20 hydrocarbon groups include trimethylsilyloxy, triethylsilyloxy, tri-n-butylsilyloxy, triphenylsilyloxy, triisopropylsilyloxy, tert-butyldimethylsilyloxy, dimethylphenylsilyloxy, and methyldiphenylsilyloxy, and preferred are trimethylsilyloxy, triphenylsilyloxy, and triisopropylsilyloxy.

Examples of the C1-20 hydrocarbon group-substituted silyloxy are those exemplified as silyloxy groups having a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom as a substituent in the above-exemplified unsubstituted C1-20 hydrocarbon groups.

Two neighboring substituent groups among R1 to R4 and optional two neighboring substituent groups among R7 to R10 may be bonded each other to form rings, and R5 and R6 may be bonded each other to form a ring and two or three of R12, R13, and R14 may be bonded to form a ring.

Examples of the rings formed by bonding two neighboring substituent groups among R1 to R4, two neighboring substituent groups among R7 to R10, R5 and R6, and two or three of R12, R13, and R14 may be saturated or unsaturated hydrocarbon rings having a substituted or unsubstituted C1-20 hydrocarbon group. Specific examples of the rings are alicyclic C3-8 hydrocarbon rings such as cyclopropane ring, cyclobutane ring, cyclopentane ring, cycloheptane ring, or cyclooctane ring; and aromatic C6-14 hydrocarbon rings such as benzene ring, naphthalene ring, or anthracene ring.

Examples of the unsubstituted hydrocarbon group represented by R12, R13, and R14 include an C1-10 alkyl such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, or decyl; an C2-10 alkenyl such as vinyl, aryl, propenyl, 2-methyl-2-propenyl, homoallyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, or decenyl; and an C7-12 aralkyl such as benzyl, (4-methylphenyl)methyl, and (2,4,6-trimethylphenyl)methyl. R11 is a C1-10 alkyl including the examples as defined above.

Examples of the substituted hydrocarbon include an alkyl substituted with an alkoxy or alkoxyalkyl such as methoxymethyl or methoxyethoxymethyl, and also hydrocarbon groups derived from the above-exemplified hydrocarbon groups by substituting a halogen atom for hydrogen, and specific examples of halogen-substituted hydrocarbon groups include 2-chloro-2-propenyl.

Examples of the tri-substituted silyl include trimethylsilyl, triethylsilyl, tri-n-propylsilyl, triisopropylsilyl, tri-n-butylsilyl, tri-sec-butylsilyl, tri-tert-butylsilyl, triisobutylsilyl, tert-butyldimethylsilyl, tri-n-pentylsilyl, tri-n-hexylsilyl, tricyclohexylsilyl, and triphenylsilyl. R11 is preferably methyl in that the metallocene compound of formula (3) is produced in a higher yield.

Examples of the silicon-substituted cyclopentadiene compound of formula (1) of the invention include 1-methoxy-2-[1-(3-trimethylsilyl-cyclopenta-1,4-dienyl)-1-methyl-ethyl]benzene, 1-methoxy-4,6-dimethyl-2-[1-(3-trimethylsilyl-cyclopenta-1,4-dienyl)-1-methyl-ethyl]benzene, 6-tert-butyl-1-methoxy-4-methyl-2-[1-(3-trimethylsilylcyclopenta-1,4-dienyl)-1-methyl-ethyl]benzene, 1-methoxy-2-phenyl-6-[1-(3-trimethylsilyl-cyclopenta-1, 4-dienyl)-1-methyl-ethyl]benzene, 1-tert-butyldimethylsilyl-2-methoxy-5-methyl-3-[1-(3-trimethylsilyl-cyclopenta-1,4-dienyl)-1-methylethyl]benzene, 2-methoxy-5-methyl-1-trimethylsilyl-3-[1-(3-trimethylsilyl-cyclopenta-1,4-dienyl)-1-methyl-ethyl]benzene, 6-tert-butyl-1,4-dimethoxy-2-[1-(3-trimethylsilyl-cyclopenta-1,4-dienyl)-1-methyl-ethyl]benzene, 5-tert-butyl-1-chloro-4-methoxy-3-[1-(3-trimethylsilyl-cyclopenta-1,4-dienyl)-1-methyl-ethyl]benzene, 6-tert-butyl-1-methoxy-2-[1-(3-trimethylsilyl-cyclopenta-1,4-dienyl)-1-methyl-ethyl]benzene, and isomers of these exemplified compounds which isomers have the double bond of the cyclopentadiene ring at different positions and isomers of these exemplified compounds which isomers have the trimethylsilyl group at a different position of the cyclopentadiene ring;

Silicon of the silicon-substituted cyclopentadiene compound of formula (1) of the invention may be bonded to any carbon atom of the cyclopentadiene ring and double bond of the cyclopentadiene ring may be at any position. For example, the following substituting styles for cyclopentadiene and silicon can be exemplified and the silicon-substituted cyclopentadiene compound of the invention may be a mixture of any of these substituted compounds.

The silicon-substituted cyclopentadiene compound of formula (1) of the invention can be produced by, for example, a process which comprises reacting a substituted cyclopentadiene compound of formula (4) wherein R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, and R11 independently denote the same as described above, and the double bond of the cyclopentadiene may be at any position, with a base and successively reacting the resulting product with a halogenated silyl compound of formula (5) wherein R12, R13, and R14 independently denote same as described above and Y denote a halogen atom, reference to Non-Patent Document 1.

Example of the transition metal compound of formula (2) are a titanium halide such as titanium tetrachloride, titanium trichloride, titanium tetrabromide, and titanium tetraiodide; amido titanium such as tetrakis(dimethylamino)titanium, dichlorobis(dimethylamino)titanium, trichloro(dimethylamino)titanium, or tetrakis(diethylamino)titanium; an alkoxytitanium such as tetraisopropoxytitanium, tetra(n-butoxy)titanium, dichlorodiisopropoxytitanium, or trichloroisopropoxytitanium; and

Examples of the metallocene compound of formula (3) include methylene(cyclopentadienyl)(3,5-dimethyl-2-phenoxy)titanium dichloride, methylene(cyclopentadienyl)(3-tert-butyl-2-phenoxy)titanium dichloride, methylene(cyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titanium dichloride, methylene(cyclopentadienyl)(3-phenyl-2-phenoxy)titanium dichloride, methylene(cyclopentadienyl)(3-tert-butyldimethylsilyl-5-methyl-2-phenoxy)titanium dichloride, methylene(cyclopentadienyl)(3-trimethylsilyl-5-methyl-2-phenoxy)titanium dichloride, methylene(cyclopentadienyl)(3-tert-butyl-5-methoxy-2-phenoxy)titanium dichloride, methylene(cyclopentadienyl)(3-tert-butyl-5-chloro-2-phenoxy)titanium dichloride,

The metallocene compound of formula (3) of the invention can be produced by reaction of the silicon-substituted cyclopentadiene compound of formula (1) and the transition metal complex of formula (2) in a solvent containing an aromatic hydrocarbon.

It has been known that the metallocene compound of formula (3) can be obtained by, for example, a method similar to the method (e.g., the above-mentioned Non-Patent Document 1) of causing reaction of a brominated phenol and a base and successively reacting the resulting product with dimethylfulvene, and thereafter with titanium tetrachloride, or the method (e.g., the above-mentioned Non-Patent Document 1) of heating a compound obtained by bonding methoxyphenol and cyclopentadienyltitanium trichloride at 110ºC under reduced pressure, however the technique of the invention is more advantageous in terms of the yield.

The metallocene compound of formula (3) of the invention can be produced also by reacting a substituted cyclopentadiene compound of formula (4) and a base in a solvent containing an aromatic hydrocarbon, successively reacting the resulting reaction product with a halogenated silyl compound of formula (5), and without refining the produced substance, and reacting the resulting substance with a transition metal compound of formula (2).

The base that may be used in these production processes are bases capable of substract a proton from a cyclopentadiene ring, and of which examples are organic alkali metal compounds such as organic lithium compounds, e.g., methyllithium, ethyllithium, n-butyllithium, sec-butyllithium, tert-butyllithium, lithium trimethylsilylacetylide, lithium acetylide, trimethylsilylmethyllithium, vinyllithium, phenyllithium, and allyllithium and the use amount of the base is generally in a range from 0.5 to 5 moles and preferably in a range from 1.1 to 2 moles to 1 mole of the substituted cyclopentadiene compound of formula (4).

The substituted cyclopentadiene compound of formula (4) is obtained, for example, by a method similar to the method (e.g., the above-mentioned Patent Document 1) of causing reaction of a halogenated aryl compound with an organic alkali metal compound or metal magnesium and thereafter successively reaction of the reaction product with a cyclopentadienylidene compound.

Examples of the substituted cyclopentadiene compound of formula (4) are 2-[(cyclopenta-1,4-dienyl)methyl]-1-methoxybenzene, 2-[(cyclopenta-1,4-dienyl)methyl]-1-methoxy-4,6-dimethylbenzene, 2-tert-butyl-6-[(cyclopenta-1,4-dienyl)methyl]-1-methoxy-4-methylbenzene, 6-[(cyclopenta-1,4-dienyl)methyl]-1-methoxy-2-phenylbenzene, 1-tert-butyldimethylsilyl-3-[(cyclopenta-1,4-dienyl)methyl]-2-methoxy-5-methoxybenzene, 3-[(cyclopenta-1,4-dienyl)methyl]-2-methoxy-5-methyl-1-trimethylsilylbenzene, 2-tert-butyl-6-[(cyclopenta-1,4-dienyl)methyl]-1,4-dimethoxybenzene, 3-tert-butyl-1-chloro-5-[(cyclopenta-1,4-dienyl)methyl]-4-methoxybenzene, 2-tert-butyl-6-[(cyclopenta-1,4-dienyl)methyl]-1-methoxybenzene,

2-[1-(cyclopenta-1,4-dienyl)-1-methyl-ethyl]-1-methoxybenzene, 2-[1-(cyclopenta-1,4-dienyl)-1-methylethyl]-1-methoxy-4,6-dimethylbenzene, 6-tert-butyl-2-[1-(cyclopenta-1,4-dienyl)-1-methyl-ethyl]-1-methoxy-4-methylbenzene, 6-[1-(cyclopenta-1,4-dienyl)-1-methylethyl]-1-methoxy-2-phenylbenzene, 1-tert-butyldimethylsilyl-3-[1-(cyclopenta-1,4-dienyl)-1-methylethyl]-2-methoxy-5-methoxybenzene, 3-[1-(cyclopenta-1,4-dienyl)-1-methyl-ethyl]-2-methoxy-5-methyl-1-trimethylsilylbenzene, 6-tert-butyl-2-[1-(cyclopenta-1,4-dienyl)-1-methyl-ethyl]-1,4-dimethoxybenzene, 5-tert-butyl-1-chloro-3-[1-(cyclopenta-1,4-dienyl)-1-methyl-ethyl]-4-methoxybenzene, 6-tert-butyl-2-[1-(cyclopenta-1,4-dienyl)-1-methyl-ethyl]-1-methoxybenzene,

1-methoxy-2-[1-(4-methylcyclopenta-1,4-dienyl)-1-methyl-ethyl]benzene, 1-methoxy-4,6-dimethyl-2-[1-(4-methylcyclopenta-1,4-dienyl)-1-methyl-ethyl]benzene, 6-tert-butyl-1-methoxy-4-methyl-2-[1-(4-methylcyclopenta-1,4-dienyl)-1-methyl-ethyl]benzene, 1-methoxy-6-[1-(4-methylcyclopenta-1,4-dienyl)-1-methyl-ethyl]-2-phenylbenzene, 1-tert-butyldimethylsilyl-2-methoxy-5-methyl-3-[1-(4-methylcyclopenta-1,4-dienyl)-1-methylethyl]benzene, 2-methoxy-5-methyl-3-[1-(4-methylcyclopenta-1,4-dienyl)-1-methyl-ethyl]-1-trimethylsilylbenzene, 6-tert-butyl-1,4-dimethoxy-2-[1-(4-methylcyclopenta-1,4-dienyl)-1-methyl-ethyl]benzene, 5-tert-butyl-1-chloro-4-methoxy-3-[1-(4-methylcyclopenta-1,4-dienyl)-1-methylethyl]benzene, 6-tert-butyl-1-methoxy-2-[1-(4-methylcyclopenta-1,4-dienyl)-1-methyl-ethyl]benzene,

2-[1-(4-tert-butylcyclopenta-1,4-dienyl)-1-methylethyl]-1-methoxybenzene, 2-[1-(4-tert-butylcyclopenta-1,4-dienyl)-1-methyl-ethyl]-1-methoxy-4,6-dimethyl-benzene, 6-tert-butyl-2-[1-(4-tert-butylcyclopenta-1,4-dienyl)-1-methyl-ethyl]-1-methoxy-4-methylbenzene, 6-[1-(4-tert-butylcyclopenta-1,4-dienyl)-1-methyl-ethyl]-1-methoxy-2-phenylbenzene, 1-tert-butyldimethylsilyl-3-[1-(4-tert-butylcyclopenta-1,4-dienyl)-1-methyl-ethyl]-2-methoxy-5-methyl-benzene, 3-[1-(4-tert-butylcyclopenta-1,4-dienyl)-1-methyl-ethyl]-2-methoxy-5-methyl-1-trimethylsilylbenzene, 6-tert-butyl-2-[1-(4-tert-butylcyclopenta-1,4-dienyl)-1-methyl-ethyl]-1,4-dimethoxybenzene, 5-tert-butyl-1-chloro-3-[1-(4-tert-butylcyclopenta-1,4-dienyl)-1-methyl-ethyl]-4-methoxybenzene, 6-tert-butyl-2-[1-(4-tert-butylcyclopenta-1,4-dienyl)-1-methyl-ethyl]-1-methoxybenzene,

1-methoxy-2-[1-(2,3,4,5-tetramethylcyclopenta-1,4-dienyl)-1-methyl-ethyl]benzene, 1-methoxy-4,6-dimethyl-2-[1-(2,3,4,5-tetramethylcyclopenta-1,4-dienyl)-1-methylethyl]benzene, 6-tert-butyl-1-methoxy-4-methyl-2-[1-(2,3,4,5-tetramethylcyclopenta-1,4-dienyl)-1-methylethyl]benzene, 1-methoxy-2-phenyl-6-[1-(2,3,4,5-tetramethylcyclopenta-1,4-dienyl)-1-methyl-ethyl]benzene, 1-tert-butyldimethylsilyl-2-methoxy-5-methyl-3-[1-(2,3,4,5-tetramethylcyclopenta-1,4-dienyl)-1-methyl-ethyl]benzene, 2-methoxy-5-methyl-3-[1-(2,3,4,5-tetramethylcyclopenta-1,4-dienyl)-1-methyl-ethyl]-1-trimethylsilylbenzene, 6-tert-butyl-1,4-dimethoxy-2-[1-(2,3,4,5-tetramethylcyclopenta-1,4-dienyl)-1-methyl-ethyl]benzene, 5-tert-butyl-1-chloro-4-methoxy-3-[1-(2,3,4,5-tetramethylcyclopenta-1,4-dienyl)-1-methyl-ethyl]benzene, 6-tert-butyl-1-methoxy-2-[1-(2,3,4,5-tetramethylcyclopenta-1,4-dienyl)-1-methylethyl]benzene,

2-[1-(cyclopenta-1,4-dienyl)-1-ethyl-propyl]-1-methoxybenzene, 2-[1-(cyclopenta-1,4-dienyl)-1-ethylpropyl]-1-methoxy-4,6-dimethyl-benzene, 6-tert-butyl-2-[1-(cyclopenta-1,4-dienyl)-1-ethyl-propyl]-1-methoxy-4-methylbenzene, 6-[1-(cyclopenta-1,4-dienyl)-1-ethylpropyl]-1-methoxy-2-phenylbenzene, 1-tert-butyldimethylsilyl-3-[1-(cyclopenta-1,4-dienyl)-1-ethylpropyl]-2-methoxy-5-methyl-benzene, 3-[1-(cyclopenta-1,4-dienyl)-1-ethyl-propyl]-2-methoxy-5-methyl-1-trimethylsilylbenzene, 6-tert-butyl-2-[1-(cyclopenta-1,4-dienyl)-1-ethyl-propyl]-1,4-dimethoxybenzene, 5-tert-butyl-1-chloro-3-[1-(cyclopenta-1,4-dienyl)-1-ethyl-propyl]-4-methoxybenzene, 6-tert-butyl-2-[1-(cyclopenta-1,4-dienyl)-1-ethyl-propyl]-1-methoxybenzene,

2-[1-(cyclopenta-1,4-dienyl)-1,1-diphenylmethyl]-1-methoxybenzene, 2-[1-(cyclopenta-1,4-dienyl)-1,1-diphenylmethyl]-1-methoxy-4,6-dimethyl-benzene, 6-tert-butyl-2-[1-(cyclopenta-1,4-dienyl)-1,1-diphenylmethyl]-1-methoxy-4-methylbenzene, 2-[1-(cyclopenta-1,4-dienyl)-1,1-diphenylmethyl]-1-methoxy-6-phenylbenzene, 1-tert-butyldimethylsilyl-3-[1-(cyclopenta-1,4-dienyl)-1,1-diphenylmethyl]-2-methoxy-5-methyl-benzene, 3-[(cyclopenta-1,4-dienyl)-1,1-diphenylmethyl]-2-methoxy-5-methyl-1-trimethylsilylbenzene, 6-tert-butyl-2-[(cyclopenta-1,4-dienyl)-1,1-diphenylmethyl]-1,4-dimethoxybenzene, 5-tert-butyl-1-chloro-3-[(cyclopenta-1,4-dienyl)-1,1-diphenylmethyl]-4-methoxybenzene, 6-tert-butyl-2-[(cyclopenta-1,4-dienyl)-1,1-diphenylmethyl]-1-methoxybenzene, compounds obtained by replacing methoxy of these exemplified compounds with ethoxy, and isopropoxy. Furthermore, compounds replacing methoxy of these exemplified compounds with benzoyloxy, trimethylsilyloxy, tert-butyldimethylsilyloxy, and methoxymethoxy are disclosed. Compounds obtained by replacing cyclopenta-1,4-dienyl of these exemplified compounds with dimethylcyclopenta-1,4-dienyl, trimethylcyclopenta-1,4-dienyl, n-butylcyclopenta-1,4-dienyl, indenyl, and fluorenyl, compounds obtained by replacing 1-methoxybenzene of these exemplified compounds with 1-methoxy-6-methylbenzene, 1-methoxy-4,6-di-tert-butylbenzene, 1-methoxy-4-methyl-6-phenylbenzene, 1-tert-butyldimethylsilyl-2-methoxybenzene, and 2-methoxy-1-trimethylsilylbenzene, and isomers of these exemplified compounds in which the double bond of the cyclopentadiene ring is at different positions.

Examples of the halogenated silyl compound of formula (5) are chlorotrimethylsilane, chlorotriethylsilane, chlorotriisopropylylsilane, chlorotri-n-propylsilane, chlorotri-n-butylsilane, chlorotri-sec-butylsilane, chlorotri-tert-butylsilane, tert-butyldimethylchlorosilane, dimethylphenylchlorosilane, chloromethylsilacyclohexane, chloromethylsilacyclobutane, chloromethylsilacyclopentane, chlorotriphenylsilane, 3-chloropropyldimethylchlorosilane, dichlorodimethylsilane, methyltrichlorosilane, tetrachlorosilane, and compounds obtained by replacing chlorine of these exemplified compounds with fluorine, bromine, and iodine and preferably chlorotrimethylsilane and tert-butyldimethylchlorosilane.

The metallocene compound of formula (3) can be produced in a particularly high yield in a solvent containing an aromatic hydrocarbon. As the aromatic hydrocarbon is exemplified benzene which may have a substituent such as a halogen atom, a C1-5 alkyl, or a C1-5 alkoxy and practical examples are benzene, toluene, o-xylene, m-xylene, p-xylene, ethylbenzene, n-propylbenzene, cumene, n-butylbenzene, sec-butylbenzene, isobutylbenzene, tert-butylbenzene, amylbenzene, isoamylbenzene, 2-ethyltoluene, 3-ethyltoluene, 4-ethyltoluene, mesitylene, anisole, 2-methylanisole, 3-methylanisole, 4-methylanisole, phenetole, propyl phenyl ether, butyl phenyl ether, pentyl phenyl ether, chlorobenzene, dichlorobenzene, and trichlorobenzene, preferably benzene, toluene and xylene and particularly preferably toluene. These aromatic hydrocarbon solvents may be used alone while mixtures of the organic solvent containing further one or more organic solvents that are inert to the reaction such as aliphatic hydrocarbon solvents, e.g., pentane, hexane, heptane, octane and the like; ether solvents such as diethyl ether, tetrahydrofuran, 1,4-dioxane or the like; and halogenated solvents such as dichloromethane, dichloroethane or the like may be used. The amount of the aromatic hydrocarbon solvent that may be used is generally in a range of about 1 to 200 parts by weight and preferably in a range of about 3 to 50 parts by weight per 1 part by weight of the silicon-substituted cyclopentadiene compound of formula (1), and the aromatic hydrocarbon solvent may be used as a mixture of organic solvents containing an organic solvent that is inert to the reaction and the aromatic hydrocarbon solvent, preferably in the amount of 50% by weight of the mixture.

The reaction temperature is generally -100ºC to a boiling point of the solvent, preferably -80 to 100ºC, more preferably -10 to 100ºC, and even more preferably -10 to 60ºC.

After completion of the reaction, the metallocene compound of formula (3) can be obtained, for example, by removal of insoluble solid matter and followed by evaporation of the solvent, or it can be obtained from a filtrate after removal of the insoluble matter, which filtrate is obtained by concentration of the reaction mixture. If necessary, the obtained metallocene compound can be purified by coventional method such as recrystallization, sublimation or the like.

The metallocene compound of formula (3) produced by the above-mentioned method can be used for polymerization reaction while being reacted with an activation cocatalyst. Examples of the activation cocatalyst include compounds such as a zinc compound, an aluminum compound, or a boron compound which may be used commonly in polymerization reaction.

The activation cocatalyst is preferably an aluminum compound and a non-aluminum compound which is coupled with a transition metal to form an ion complex and the compounds may be used alone or in combination for polymerization reaction while being reacted with a metal complex.

The metallocene compound produced by the invention is effective in, for example, polymerization reaction of olefins and has industrial advantage.

Examples

Hereinafter, the invention will be described more in detail along with Examples, however it is not intended that the invention be limited to the illustrated Examples.

[NMR measurement conditions]

Example 1 Synthesis of isopropylidene(cyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titanium dichloride

Under nitrogen atmosphere, a toluene solution (27 mL) containing titanium tetrachloride (0.67 g, 3.52 mmol) was stirred at -50ºC. A solution of 6-tert-butyl-2-[1-(3-trimethylsilylcyclopenta-1,4-dienyl)-1-methyl-ethyl]-1-methoxy-4-methylbenzene (1.26 g, 3.52 mmol) in toluene (10 mL) was added dropwise to the toluene solution. After the mixture was warmed to a room temperature, the solution was heated at 90ºC for 2 hours. After being cooled to a room temperature, the solution was filtered through Celite and the obtained filtrate was concentrated. Hexane was added to the mixture to obtain isopropylidene(cyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titanium dichloride as a brown solid (0.68 g, yield 49.7%).
1H-NMR (CDCl3, d(ppm)): 1.42 (s, 9H, Ar-tBu), 1.60 (s, 6H, Me2C), 2.39 (s, 3H, Ar-Me), 6.12 (t, J = 2.7Hz, 2H, Cp), 6.97 (t, J = 2.7 Hz, 2H, Cp), 7.22 (s, 1H, Ar), 7.26 (s, 1H, Ar)
Mass spectrum (EI, m/z): 386 (M+), 371, 335

Example 2

In nitrogen atmosphere, 6-tert-butyl-2-[1-(cyclopenta-1,4-dienyl)-1-methyl-ethyl]-1-methoxy-4-methylbenzene (1.00 g, 3.52 mmol) was dissolved in toluene (30 mL) and cooled to 0ºC. After that, a solution of n-butyllithium in hexane (2.73 mL, 1.58 M, 4.31 mmol) was added dropwise to the obtained toluene solution and stirred at 50ºC for 1 hour. After the reaction mixture was cooled to 0ºC, a solution of chlorotrimethylsilane (0.47 g, 4.31 mmol) in toluene (5.78 mL) was added dropwide and stirred at 50ºC for 1 hour. After the reaction mixture was cooled to -50ºC, a solution obtained by dissolving titanium tetrachloride (0.82 g, 4.31 mmol) in toluene (5.78 mL) was added dropwise and the mixture was heated to a room temperature. After that, the mixture was heated at 90ºC for 2 hours and successively cooled to a room temperature and the reaction mixture was filtered through Celite and the obtained filtrate was concentrated. Hexane was added to the mixture to obtain isopropylidene(cyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titanium dichloride as a brown solid (0.80 g, yield 58.8%).

Example 3

The reaction was carried out in the same manner as Example 2, except that 0.52 g (4.74 mmol) of chlorotrimethylsilane was used to obtain isopropylidene(cyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titanium dichloride as a brown solid (0.73 g, yield 53.6%).

Example 4

The reaction was carried out in the same manner as Example 3, except that the addition temperature of titanium tetrachloride was changed to 0ºC and the heating temperature after addition of titanium tetrachloride was changed to 70ºC to obtain isopropylidene(cyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titanium dichloride as a brown solid (0.65 g, yield 48.1%).

Example 5

The reaction was carried out in the same manner as Example 3, except that the addition temperature of titanium tetrachloride was changed to 0ºC and the heating temperature after addition of titanium tetrachloride was changed to 50ºC to obtain isopropylidene(cyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titanium dichloride as a brown solid (0.77 g, yield 56.5%).

Example 6

In nitrogen atmosphere, 6-tert-butyl-2-[1-(cyclopenta-1,4-dienyl)-1-methyl-ethyl]-1-methoxy-4-methylbenzene (1.00 g, 3.52 mmol) was dissolved in toluene (30 mL) and cooled to 0ºC. After that, a solution of n-butyllithium in hexane (2.80 mL, 1.58 M, 4.42 mmol) was added dropwise to the obtained toluene solution and stirred at 50ºC for 1 hour. After the reaction mixture was cooled to 0ºC, a solution containing chlorotrimethylsilane (0.48 g, 4.42 mmol) in toluene (5.78 mL) was added dropwise and stirred at 50ºC for 1 hour. After the reaction mixture was cooled to 0ºC, a solution obtained by dissolving titanium tetrachloride (0.84 g, 4.42 mmol) in toluene (5.78 mL) was added dropwise and the mixed solution was warmed to a room temperature. After that, the solution was heated at 50ºC for 2 hours and successively cooled to a room temperature and the reaction mixture was filtered through Celite and the obtained filtrate was concentrated. The obtained filtrate was subjected to 1H-NMR analysis (toluene-d8) using dibromoethane as an internal standard to measure the content of isopropylidene(cyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titanium dichloride (0.89 g, yield 65.8%).
1H-NMR (toluene-d8, d(ppm)): 1.23 (s, 6H, Me2C), 1.52 (s, 9H, Ar-tBu), 2.09 (s, 3H, Ar-Me), 5.47 (t, J = 2.7Hz, 2H, Cp), 6.29 (t, J = 2.7 Hz, 2H, Cp), 6.97-7.09 (2H, Ar)

Example 7

The reaction was carried out in the same manner as Example 6, except that 1.01 g (5.30 mmol) of titanium tetrachloride was used. The content of isopropylidene(cyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titanium dichloride was confirmed by 1H-NMR analysis (0.94 g, yield 69.2%).

Example 8

The reaction was carried out in the same manner as Example 6, except that the method was changed by addition of the reaction mixture to the titanium tetrachloride solution. The content of isopropylidene(cyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titanium dichloride was confirmed by 1H-NMR analysis (0.84 g, yield 61.8%).

Example 9

The reaction was carried out in the same manner as Example 6, except that the amount of toluene to dissolve 6-tert-butyl-2-[1-(cyclopenta-1,4-dienyl)-1-methyl-ethyl]-1-methoxy-4-methylbenzene was changed to 15 mL. The content of isopropylidene(cyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titanium dichloride was confirmed by 1H-NMR analysis (0.85 g, yield 62.7%).

Example 10

The reaction was carried out in the same manner as Example 9, except that neat chlorotrimethylsilane was added dropwise as it was without being dissolved in toluene. The content of isopropylidene(cyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titanium dichloride was confirmed by 1H-NMR analysis (0.93 g, yield 69.0%).

Example 11

The reaction was carried out in the same manner as Example 10, except that addition temperature of chlorotrimethylsilane was changed to 50ºC. The content of isopropylidene(cyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titanium dichloride was confirmed by 1H-NMR analysis (0.87 g, yield 63.8%).

Example 12

The reaction was carried out in the same manner as Example 11, except that 1.01 g (5.30 mmol) of titanium tetrachloride was used. The content of isopropylidene(cyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titanium dichloride was confirmed by 1H-NMR analysis (1.02 g, yield 75.2%).

Example 13

The reaction was carried out in the same manner as Example 7, except that 0.67 g (3.55 mmol) of titanium tetrachloride was used. The content of isopropylidene(cyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titanium dichloride was confirmed by 1H-NMR analysis (0.65 g, yield 47.7%).

Example 14

The reaction was carried out in the same manner as Example 7, except that 0.75 g (3.97 mmol) of titanium tetrachloride was used. The content of isopropylidene(cyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titanium dichloride was confirmed by 1H-NMR analysis (0.67 g, yield 49.6%).

Example 15

The reaction was carried out in the same manner as Example 7, except that 0.84 g (4.42 mmol) of titanium tetrachloride was used. The content of isopropylidene(cyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titanium dichloride was confirmed by 1H-NMR analysis (0.89 g, yield 65.8%).

Example 16

The reaction was carried out in the same manner as Example 7, except that 0.92 g (4.88 mmol) of titanium tetrachloride was used. The content of isopropylidene(cyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titanium dichloride was confirmed by 1H-NMR analysis (0.88 g, yield 64.5%).

Example 17

The reaction was carried out in the same manner as Example 7, except that 1.10 g (5.76 mmol) of titanium tetrachloride was used. The content of isopropylidene(cyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titanium dichloride was confirmed by 1H-NMR analysis (0.94 g, yield 69.4%).

Example 18

The reaction was carried out in the same manner as Example 7, except that 1.18 g (6.18 mmol) of titanium tetrachloride was used. The content of isopropylidene(cyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titanium dichloride was confirmed by 1H-NMR analysis (0.92 g, yield 68.1%).

Example 19 Synthesis of isopropylidene(cyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)zirconium dichloride

In nitrogen atmosphere, 6-tert-butyl-2-[1-(cyclopenta-1,4-dienyl)-1-methyl-ethyl]-1-methoxy-4-methylbenzene (3.00 g, 10.55 mmol) was dissolved in toluene (43 mL) and cooled to 0ºC. After that, a solution of n-butyllithium in hexane (9.48 mL, 1.58 M, 14.98 mmol) was added dropwise to the obtained toluene solution and stirred at 50ºC for 1 hour. Chlorotrimethylsilane (1.63 g, 14.98 mmol) was added dropwise and stirred at 50ºC for 1 hour. After the reaction mixture was cooled to 0ºC, the reaction mixture was added dropwise to a suspension of zirconium tetrachloride (4.18 g, 17.93 mmol) in toluene (9 mL) and the mixture was heated to a room temperature. After that, the mixture was heated at 60ºC for 2 hours and successively cooled to a room temperature and the reaction mixture was filtered through Celite and the obtained filtrate was concentrated to obtain isopropylidene(cyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)zirconium dichloride as a brown solid.

The obtained mixture was subjected to 1H-NMR analysis using dibromoethane as an internal standard to measure the content of isopropylidene(cyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)zirconium dichloride (0.28 g, yield 6.2%).
1H-NMR (CDCl3, d(ppm)): 1.41 (s, 9H, Ar-tBu), 1.59 (s, 6H, Me2C), 2.40 (s, 3H, Ar-Me), 6.10 (t, J = 2.7Hz, 2H, Cp), 6.80 (t, J = 2.7 Hz, 2H, Cp), 7.20 (s, 1H, Ar), 7.28 (s, 1H, Ar)
Mass spectrum (EI, m/z): 430 (M+), 415, 377

Example 20 Synthesis of isopropylidene(cyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)hafnium dichloride

In nitrogen atmosphere, 6-tert-butyl-2-[1-(cyclopenta-1,4-dienyl)-1-methyl-ethyl]-1-methoxy-4-methylbenzene (3.00 g, 10.55 mmol) was dissolved in toluene (43 mL) and cooled to 0ºC. After that, a solution of n-butyllithium solution in hexane (9.48 mL, 1.58 M, 14.98 mmol) was added dropwise to the obtained toluene solution and stirred at 50ºC for 1 hour Chlorotrimethylsilane (1.63 g, 14.98 mmol) was added dropwise and stirred at 50ºC for 1 hour. After the reaction mixture was cooled to 0ºC, the reaction mixture was added dropwise to a suspension of hafnium tetrachloride (5.74 g, 17.93 mmol) in toluene (9 mL) and the mixture was warmed to a room temperature. After that, the solution was heated at 60ºC for 2 hours and successively cooled to a room temperature and the reaction mixture was filtered through Celite and the obtained filtrate was concentrated to obtain isopropylidene(cyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)hafnium dichloride as a brown solid. The obtained mixture was subjected to 1H-NMR analysis using dibromoethane as an internal standard to measure the content of isopropylidene(cyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)hafnium dichloride (3.61 g, yield 66.1%).
1H-NMR (CDCl3, d(ppm)): 1.38 (s, 9H, Ar-tBu), 1.60 (s, 6H, Me2C), 2.38 (s, 3H, Ar-Me), 6.10 (t, J = 2.7Hz, 2H, Cp), 6.70 (t, J = 2.7 Hz, 2H, Cp), 7.10 (s, 1H, Ar), 7.21 (s, 1H, Ar)
Mass spectrum (EI, m/z): 518 (M+), 503, 467

Comparative Example 1

In nitrogen atmosphere, 6-tert-butyl-2-[1-(cyclopenta-1,4-dienyl)-1-methyl-ethyl]-1-methoxy-4-methylbenzene (1.00 g, 3.52 mmol) was dissolved in toluene (35 mL) and cooled to 0ºC. After that, a solution of n-butyllithium in hexane (2.89 mL, 1.58 M, 4.57 mmol) was added dropwise to the obtained toluene solution and stirred at 50ºC for 4 hours. After the reaction mixture was cooled to -50ºC, a solution of titanium tetrachloride (0.67 g, 3.52 mmol) in toluene (8.09 mL) was added dropwise to the reaction mixture and the mixture was heated to a room temperature. After that, the mixture was heated at 90ºC for 2 hours and successively cooled to a room temperature and the reaction mixture was filtered through Celite and the obtained filtrate was concentrated. Hexane was added to the obtained filtrate to obtain isopropylidene(cyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titanium dichloride as a brown solid (0.46 g, yield 33.6%)

Comparative Example 2

In nitrogen atmosphere, 6-tert-butyl-2-[1-(cyclopenta-1,4-dienyl)-1-methyl-ethyl]-1-methoxy-4-methylbenzene (1.00 g, 3.52 mmol) was dissolved in toluene (25 mL) and cooled to 0ºC. After that, a solution of n-butyllithium in hexane (2.80 mL, 1.58 M, 4.42 mmol) was added dropwise to the obtained toluene solution and stirred at 50ºC for 1 hour. After the reaction mixture was cooled to 0ºC, a solution of titanium tetrachloride (0.84 g, 3.52 mmol) in toluene (11.56 mL) was added dropwise to the reaction mixture and the mixture was heated to a room temperature. After that, the mixture was heated at 50ºC for 2 hours, and successively cooled to a room temperature and the reaction mixture was filtered through Celite and the obtained filtrate was concentrated. The concentrated filtrate was analyzed by 1H-NMR to find it was complicated mixture and production of isopropylidene(cyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titanium dichloride was slight (0.06 g, yield 4.2%)

 A process for producing a metallocene compound of formula (3); wherein R1, R2, R3 and R4 independently denote a hydrogen atom, a halogen atom, a substituted or unsubstituted C1-20 alkyl, a substituted or unsubstituted C6-20 aryl, or a substituted or unsubstituted C7-20 aralkyl; R5, R6, R7, R8, and R9 independently denote a hydrogen atom, a halogen atom, a substituted or unsubstituted C1-20 alkyl, a substituted or unsubstituted C1-20 alkoxy, a substituted or unsubstituted C6-20 aryl, a substituted or unsubstituted C6-20 aryloxy, a substituted or unsubstituted C7-20 aralkyl, a substituted or unsubstituted C7-20 aralkyloxy, a silyl substituted with a substituted or unsubstituted C1-20 hydrocarbon group, a silyloxy substituted with a substituted or unsubstituted C1-20 hydrocarbon group, or an amino substituted with a substituted or unsubstituted C1-20 hydrocarbon group; R10 denotes a halogen atom, a substituted or unsubstituted C1-20 alkyl, a substituted or unsubstituted C1-20 alkoxy, a substituted or unsubstituted C6-20 aryl, a substituted or unsubstituted C6-20 aryloxy, a substituted or unsubstituted C7-20 aralkyl, a substituted or unsubstituted C7-20 aralkyloxy, a silyl substituted with a substituted or unsubstituted C1-20 hydrocarbon group, a silyloxy substituted with a substituted or unsubstituted C1-20 hydrocarbon group, or an amino substituted with a substituted or unsubstituted C1-20 hydrocarbon group; M denotes a transition metal atom of Group 4 of the Periodic Table; X5 and X6 may be same or different and independently denote a hydrogen atom, a halogen atom, a substituted or unsubstituted C1-20 alkyl, a substituted or unsubstituted C1-20 alkoxy, a substituted or unsubstituted C6-20 aryl, a substituted or unsubstituted C6-20 aryloxy, a substituted or unsubstituted C7-20 aralkyl, a substituted or unsubstituted C7-20 aralkyloxy, or an amino substituted with a substituted or unsubstituted C1-20 hydrocarbon group; each neighboring groups of R1, R2, R3 and R4 may be optionally bonded to each other to form a ring; R5 and R6 may be bonded to each other to form a ring; and each neighboring groups of R7, R8, R9 and R10 may be optionally bonded to each other to form a ring, which process comprises reacting a silicon-substituted cyclopentadiene compound of formula (1); wherein R1 to R10 independently denote same as described above; R11 denotes a C1-10 alkyl ; R12, R13, and R14 independently denote a halogen atom or a substituted or unsubstituted hydrocarbon group; two or three of R12, R13, and R14may be bonded to one another to form a ring; silicon may be bonded with any one of carbon atoms of the cyclopentadiene ring; and the position of the double bonds of the cyclopentadiene ring may be at optional positions, with a transition metal compound of formula (2); wherein M denotes same as described above; X2, X2, X3, and X4 may be same or different and independently denote a hydrogen atom, a halogen atom, a substituted or unsubstituted C1-20 alkyl, a substituted or unsubstituted C1-20 alkoxy, a substituted or unsubstituted C6-20 aryl, a substituted or unsubstituted C6-20 aryloxy, a substituted or unsubstituted C7-20 aralkyl, a substituted or unsubstituted C7-20 aralkyloxy, or an amino substituted with a substituted or unsubstituted C1-20 hydrocarbon group; and n denotes 0 or 1, in a solvent containing an aromatic hydrocarbon. A process for producing a metallocene compound of formula (3) according to claim 1, which comprises
reacting a substituted cyclopentadiene compound of formula (4); wherein R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, and R11 independently denote the same as described in claim 1 and the double bonds of the cyclopentadiene ring may be at optional positions, with a base in a solvent containing an aromatic hydrocarbon, reacting the resulting with a silyl halide compound of formula (5); wherein R12,R13, and R14 independently denote the same as described in claim 1, and Y denotes a halogen atom, and reacting the resulting product, without refining, with a transition metal compound of formula (2); wherein M, X1, X2, X3, X4, and n independently denote the same as defined in claim 1. The production process according to claim 1 or 2, wherein the aromatic hydrocarbon is benzene or substituted benzene having, as a substituent, a halogen atom, a C1-5 alkyl, or a C1-5 alkoxy The production process according to any one of claims 1 to 3, wherein the reaction of the silicon-substituted cyclopentadiene compound of formula (1) with the transition metal compound of formula (2) is carried out at a reaction temperature in a range from -10ºC to 100ºC. The production process according to any one of claims 1 to 4, wherein the transition metal compound of formula (2) is titanium tetrachloride and the halogenated silyl compound of formula (5) is chlorotrimethylsilane. The production process according to claim 1, wherein 1.1 moles or more of the transition metal compound of formula (2) is used per 1 mole of the silicon-substituted cyclopentadiene compound of formula (1). The production process according to claim 2, wherein 1.1 moles or more of the transition metal compound of formula (2) is used per 1 mole of the substituted cyclopentadiene compound of formula (4). Ein Verfahren zur Herstellung einer Metallocenverbindung der Formel (3): wobei R1, R2, R3 und R4 unabhängig voneinander ein Wasserstoffatom, ein Halogenatom, ein substituiertes oder unsubstituiertes C1-20-Alkyl, ein substituiertes oder unsubstituiertes C6-20-Aryl oder ein substituiertes oder unsubstituiertes C7-20-Aralkyl bezeichnen;
R5, R6, R7, R8 und R9 unabhängig voneinander ein Wasserstoffatom, ein Halogenatom, ein substituiertes oder unsubstituiertes C1-20-Alkyl, ein substituiertes oder unsubstituiertes C1-20-Alkoxy, ein substituiertes oder unsubstituiertes C6-20-Aryl, ein substituiertes oder unsubstituiertes C6-20-Aryloxy, ein substituiertes oder unsubstituiertes C7-20-Aralkyl, ein substituiertes oder unsubstituiertes C7-20-Aralkyloxy,
ein Silyl, substituiert mit einem substituierten oder unsubstituierten C1-20-Kohlenwasserstoffrest,
ein Silyloxy, substituiert mit einem substituierten oder unsubstituierten C1-20-Kohlenwasserstoffrest, oder
ein Amino, substituiert mit einem substituierten oder unsubstituierten C1-20-Kohlenwasserstoffrest, bezeichnen;
R10 ein Halogenatom, ein substituiertes oder unsubstituiertes C1-20-Alkyl, ein substituiertes oder unsubstituiertes C1-20-Alkoxy, ein substituiertes oder unsubstituiertes C6-20-Aryl, ein substituiertes oder unsubstituiertes C6-20-Aryloxy, ein substituiertes oder unsubstituiertes C7-20-Aralkyl, ein substituiertes oder unsubstituiertes C7-20-Aralkyloxy, ein Silyl, substituiert mit einem substituierten oder unsubstituierten C1-20-Kohlenwasserstoffrest,
ein Silyloxy, substituiert mit einem substituierten oder unsubstituierten C1-20-Kohlenwasserstoffrest, oder
ein Amino, substituiert mit einem substituierten oder unsubstituierten C1-20-Kohlenwasserstoffrest, bezeichnet;
M ein Übergangsmetallatom der Gruppe 4 des Periodensystems bezeichnet;
X5 und X6 gleich oder verschieden sein können und unabhängig voneinander ein Wasserstoffatom, ein Halogenatom, ein substituiertes oder unsubstituiertes C1-20-Alkyl, ein substituiertes oder unsubstituiertes C1-20-Alkoxy, ein substituiertes oder unsubstituiertes C6-20-Aryl, ein substituiertes oder unsubstituiertes C6-20-Aryloxy, ein substituiertes oder unsubstituiertes C7-20-Aralkyl, ein substituiertes oder unsubstituiertes C7-20-Aralkyloxy oder
ein Amino, substituiert mit einem substituierten oder unsubstituierten C1-20-Kohlenwasserstoffrest, bezeichnen;
wobei alle benachbarten Reste R1, R2, R3 und R4 gegebenenfalls miteinander verbunden sein können, um einen Ring zu bilden;
R5 und R6 miteinander verbunden sein können, um einen Ring zu bilden;
und alle an R7, R8, R9 und R10 angrenzenden Reste gegebenenfalls miteinander verbunden sein können, um einen Ring zu bilden,
wobei das Verfahren umfasst
Umsetzen einer mit Silicium substituierten Cyclopentadienverbindung der Formel (1): wobei R1 bis R10 unabhängig voneinander das gleiche wie vorstehend beschrieben bezeichnen; R11 ein C1-10-Alkyl bezeichnet;
R12, R13 und R14 unabhängig voneinander ein Halogenatom oder einen substituierten oder unsubstituierten Kohlenwasserstoffrest bezeichnen; zwei oder drei der Reste R12, R13 und R14 miteinander verbunden sein können, um einen Ring zu bilden; Silicium mit einem der Kohlenstoffatome des Cyclopentadienrings verbunden sein kann; und die Position der Doppelbindungen des Cyclopentadienrings an optionalen Positionen sein kann, mit
einer Übergangsmetallverbindung der Formel (2): wobei M das gleiche bezeichnet wie vorstehend beschrieben;
X1, X2, X3 und X4 gleich oder verschieden sein können und unabhängig voneinander ein Wasserstoffatom, ein Halogenatom, ein substituiertes oder unsubstituiertes C1-20-Alkyl, ein substituiertes oder unsubstituiertes C1-20-Alkoxy, ein substituiertes oder unsubstituiertes C6-20-Aryl, ein substituiertes oder unsubstituiertes C6-20-Aryloxy, ein substituiertes oder unsubstituiertes C7-20-Aralkyl, ein substituiertes oder unsubstituiertes C7-20-Aralkyloxy oder
ein Amino, substituiert mit einem substituierten oder unsubstituierten C1-20-Kohlenwasserstoffrest, bezeichnen; und
n 0 oder 1 bezeichnet,
in einem Lösungsmittel, das einen aromatischen Kohlenwasserstoff enthält. Ein Verfahren zur Herstellung einer Metallocenverbindung der Formel (3) gemäß Anspruch 1, das umfasst
Umsetzen einer substituierten Cyclopentadienverbindung der Formel (4): wobei R1, R2, R3, R4, R5, R6, R7, R8, R9, R10 und R11 unabhängig voneinander das gleiche bezeichnen wie in Anspruch 1 beschrieben und die Doppelbindungen des Cyclopentadienrings an optionalen Positionen sein können, mit
einer Base in einem Lösungsmittel, das einen aromatischen Kohlenwasserstoff enthält, Umsetzen der resultierenden Verbindung mit einer Silylhalogenidverbindung der Formel (5): wobei R12, R13 und R14 unabhängig voneinander das gleiche bezeichnen wie in Anspruch 1 beschrieben und Y ein Halogenatom bezeichnet, und
Umsetzen des resultierenden. Produkts ohne Reinigung mit einer Übergangsmetallverbindung der Formel (2): wobei M, X1, X2, X3, X4 und n unabhängig voneinander das gleiche bezeichnen wie in Anspruch 1 definiert. Das Herstellungsverfahren gemäß Anspruch 1 oder 2, wobei der aromatische Kohlenwasserstoff Benzol oder substituiertes Benzol mit einem Halogenatom, einem C1-5-Alkyl oder einem C1-5-Alkoxy als ein Substituent ist. Das Herstellungsverfahren gemäß einem der Ansprüche 1 bis 3, wobei die Reaktion der mit Silicium substituierten Cyclopentadienverbindung der Formel (1) mit der Übergangsmetallverbindung der Formel (2) bei einer Reaktionstemperatur in einem Bereich von -10 °C bis 100 °C durchgeführt wird. Das Herstellungsverfahren gemäß einem der Ansprüche 1 bis 4, wobei die Übergangsmetallverbindung der Formel (2) Titantetrachlorid ist und die halogenierte Silylverbindung der Formel (5) Chlortrimethylsilan ist. Das Herstellungsverfahren gemäß Anspruch 1, wobei 1,1 Mol oder mehr der Übergangsmetallverbindung (2), bezogen auf 1 Mol der mit Silicium substituierten Cyclopentadienverbindung der Formel (1), verwendet werden. Das Herstellungsverfahren gemäß Anspruch 2, wobei 1,1 Mol oder mehr der Übergangsmetallverbindung (2), bezogen auf 1 Mol der substituierten Cyclopentadienverbindung der Formel (4), verwendet werden. Procédé de production d'un composé métallocène de formule (3) : dans laquelle R1, R2, R3 et R4 désignent indépendamment un atome d'hydrogène, un atome d'halogène, un alkyle en C1-20 substitué ou non, un aryle en C6-20 substitué ou non, ou un aralkyle en C7-20 substitué ou non ;
R5, R6, R7, R8, et R9 désignent indépendamment un atome d'hydrogène, un atome d'halogène, un alkyle en C1-20 substitué ou non, un alcoxy en C1-20 substitué ou non, un aryle en C6-20 substitué ou non, un aryloxy en C6-20 substitué ou non, un aralkyle en C7-20 substitué ou non, un aralkyloxy en C7-20 substitué ou non,
un silyle substitué par un groupe hydrocarboné en C1-20 substitué ou non,
un silyloxy substitué par un groupe hydrocarboné en C1-20 substitué ou non, ou
un amino substitué par un groupe hydrocarboné en C1-20 substitué ou non,
R10 désigne un atome d'halogène, un alkyle en C1-20 substitué ou non, un alcoxy en C1-20 substitué ou non, un aryle en C6-20 substitué ou non, un aryloxy en C6-20 substitué ou non, un aralkyle en C7-20 substitué ou non, un aralkyloxy en C7-20 substitué ou non,
un silyle substitué par un groupe hydrocarboné en C1-20 substitué ou non,
un silyloxy substitué par un groupe hydrocarboné en C1-20 substitué ou non, ou
un amino substitué par un groupe hydrocarboné en C1-20 substitué ou non ;
M désigne un atome de métal de transition du Groupe 4 de la classification périodique ;
X5 et X6 peuvent être identiques ou différents et désignent indépendamment un atome d'hydrogène, un atome d'halogène, un alkyle en C1-20 substitué ou non, un alcoxy en C1-20 substitué ou non, un aryle en C6-20 substitué ou non, un aryloxy en C6-20
substitué ou non, un aralkyle en C7-20 substitué ou non, un aralkyloxy en C7-20 substitué ou non, ou
un amino substitué par un groupe hydrocarboné en C1-20 substitué ou non ; chacun des groupes R1, R2, R3 et R4 voisins peuvent éventuellement être liés les uns aux autres pour former un cycle ;
R5 et R6 peuvent être liés l'un à l'autre pour former un cycle ; et chacun des groupes R7, R8, R9 et R10 voisins peuvent éventuellement être liés les uns aux autres pour former un cycle,
ledit procédé comprenant
la mise en réaction d'un composé cyclopentadiène substitué par un silicium de formule (1) : dans laquelle R1 à R10 sont indépendamment tels que décrits ci-dessus ; R11 désigne un alkyle en C1-10;
R12, R13, et R14 désignent indépendamment un atome d'halogène ou un groupe hydrocarboné substitué ou non ; deux ou trois de R12, R13, et R14 peuvent être liés les uns aux autres pour former un cycle ; le silicium peut être lié à n'importe quel atome de carbone du cycle cyclopentadiène ; et les doubles liaisons du cycle cyclopentadiène peuvent être à des positions facultatives, avec
un composé de métal de transition de formule (2) : dans laquelle M est tel que décrit ci-dessus ;
X1, X2, X3, et X4 peuvent être identiques ou différents et désignent indépendamment un atome d'hydrogène, un atome d'halogène, un alkyle en C1-20 substitué ou non, un alcoxy en C1-20 substitué ou non, un aryle en C6-20 substitué ou non, un aryloxy en C6-20 substitué ou non, un aralkyle en C7-20 substitué ou non, un aralkyloxy en C7-20 substitué ou non, ou
un amino substitué par un groupe hydrocarboné en C1-20 substitué ou non ; et
n désigne 0 ou 1,
dans un solvant contenant un hydrocarbure aromatique. Procédé de production d'un composé métallocène de formule (3) selon la revendication 1, qui comprend
la mise en réaction d'un composé cyclopentadiène substitué de formule (4) : dans laquelle R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, et R11 sont indépendamment tels que décrits dans la revendication 1 et les doubles liaisons du cycle cyclopentadiène peuvent être à des positions facultatives, avec
une base dans un solvant contenant un hydrocarbure aromatique,
la mise en réaction du résultat avec un composé halogénure de silyle de formule (5) : dans laquelle R12, R13 et R14 sont indépendamment tels que décrits dans la revendication 1 et Y désigne un atome d'halogène, et
la mise en réaction du produit obtenu, sans raffinage, avec un composé de métal de transition de formule (2) : dans laquelle M, X1, X2, X3, X4 et n sont indépendamment tels que définis dans la revendication 1. Procédé de production selon la revendication 1 ou 2, dans lequel l'hydrocarbure aromatique est le benzène ou un benzène substitué ayant, comme substituant, un atome d'halogène, un alkyle en C1-5, ou un alcoxy en C1-5. Procédé de production selon l'une quelconque des revendications 1 à 3, dans lequel la réaction du composé cyclopentadiène substitué par un silicium de formule (1) avec le composé de métal de transition de formule (2) est mise en oeuvre à une température réactionnelle dans une plage de -10 à 100 °C. Procédé de production selon l'une quelconque des revendications 1 à 4, dans lequel le composé de métal de transition de formule (2) est le tétrachlorure de titane et le composé de silyle halogéné de formule (5) est le chlorotriméthylsilane. Procédé de production selon la revendication 1, dans lequel 1,1 moles ou plus du composé de métal de transition de formule (2) sont utilisées par mole du composé cyclopentadiène substitué par un silicium de formule (1). Procédé de production selon la revendication 2, dans lequel 1,1 moles ou plus du composé de métal de transition de formule (2) sont utilisées par mole du composé cyclopentadiène substitué de formule (4). REFERENCES CITED IN THE DESCRIPTION

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Patent documents cited in the description

Non-patent literature cited in the description